CN106046411B - The improved stability of polyurethane polyol blend comprising halogenated olefin blowing agents - Google Patents

The improved stability of polyurethane polyol blend comprising halogenated olefin blowing agents Download PDF

Info

Publication number
CN106046411B
CN106046411B CN201610505288.7A CN201610505288A CN106046411B CN 106046411 B CN106046411 B CN 106046411B CN 201610505288 A CN201610505288 A CN 201610505288A CN 106046411 B CN106046411 B CN 106046411B
Authority
CN
China
Prior art keywords
metal salt
metal
acetylacetonate
polyol pre
mix composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610505288.7A
Other languages
Chinese (zh)
Other versions
CN106046411A (en
Inventor
B·B·陈
J·S·科斯塔
L·阿巴斯
刘海铭
S·R·瑟沙德瑞
W·D·霍尼克
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema Inc
Original Assignee
Arkema Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arkema Inc filed Critical Arkema Inc
Publication of CN106046411A publication Critical patent/CN106046411A/en
Application granted granted Critical
Publication of CN106046411B publication Critical patent/CN106046411B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1808—Catalysts containing secondary or tertiary amines or salts thereof having alkylene polyamine groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/147—Halogen containing compounds containing carbon and halogen atoms only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0052—Organo-metallic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/02—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by the reacting monomers or modifying agents during the preparation or modification of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/127—Mixtures of organic and inorganic blowing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/022—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments premixing or pre-blending a part of the components of a foamable composition, e.g. premixing the polyol with the blowing agent, surfactant and catalyst and only adding the isocyanate at the time of foaming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/16—Unsaturated hydrocarbons
    • C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A kind of polyol pre-mix composition includes a kind of foaming agent with halogenated hydrogen alkene, a kind of polyalcohol, a kind of surfactant, a kind of carbon monoxide-olefin polymeric and a kind of metal salt.For example, the metal salt can be the carboxylate, acetylacetonate and alcoholates of a kind of metal, which is selected from the group being made of Zn, Co, Ca and Mg.For example, the metal salt can be a kind of Aliphatic monoacid of C1-C21 linear chain or branched chain or the carboxylate and/or alcoholates of monohydric alcohol, as magnesium formate, zinc octoate, calcium octoate, cobalt octoate and magnesium octoate and their mixture.For example, the metal acetylacetonates can be zinc acetylacetonate, acetylacetonate cobalt, acetylacetonate magnesium or calcium acetylacetonate.A kind of two parts system for generating thermosetting foams blend include (a) a kind of polyisocyanates and, optionally, the compatible raw material of one or more isocyanates；And (b) polyol pre-mix composition.A kind of method for generating thermosetting foams blend includes being combined the following terms: a kind of (a) polyisocyanates；And (b) polyol pre-mix composition.

Description

The improved stability of polyurethane polyol blend comprising halogenated olefin blowing agents
Divisional application explanation
The application system applying date is on 03 06th, 2012, international application no PCT/US2012/027802, into China National application number after thenational phase is 201280012689.9, the entitled " polyurethane polyol comprising halogenated olefin blowing agents The divisional application of the application for a patent for invention of the improved stability of blend ".
Invention field
The present invention relates to a kind of for stablizing the method for thermosetting foams blend, these blends include alkenyl halide hair Infusion, such as hydro-chloro fluoroolefin (HCFO) HCFO-1233zd.More particularly it relates to which a kind of be pre-mixed using polyalcohol Compositions stablize the method for thermosetting foams blend, which includes one or more metal salts.This Preparation and obtained polyurethane or polyisocyanurate foam of the invention further to the stable pre- blending.
The background of the relevant technologies
The use of Chlorofluorocarbons class (CFC) is phased out for the Montreal Protocol order of ozonosphere protection.To ozone The more " friendly " material of layer, as hydro fluorocarbons (HFC), such as HFC-134a, instead of Chlorofluorocarbons class.The compound of the latter is proved It is greenhouse gases, causes global warming, and administered by the Kyoto Protocol about climate change.The substitution material occurred Material, hydrofluoropropenes class, be shown to be it is environmentally acceptable, i.e., they have it is zero ozone depletion potential (ODP) and acceptable low Global warming potential (GWP).
The foaming agent for being currently used in thermosetting foams includes that HFC-134a, HFC-245fa, HFC-365mfc (have opposite High global warming potential) and hydro carbons such as pentane isomers class (flammable and have low-yield efficiency).Therefore, just Finding new alternative foaming agent.To halogenated hydrogen olefines material (such as hydrofluoropropenes class and/or hydrogen chlorine fluorine third Alkenes) as the sub of HFC produce interest.Intrinsic chemical instability of these materials in lower atmosphere layer provides The ozone-depleting characteristic of desired low global warming potential and zero or near zero.
In numerous applications, it provides for polyurethane or polyisocyanurate foam in the preparation being blended in advance In these components be convenient.Most typically, which is to be blended into two kinds of components in advance.These polyisocyanic acid Ester and the raw material of optional isocyanates compatibility constitute first component, commonly known as component in terms of " A- ".A kind of polyalcohol Or polyalcohol, surfactant, catalyst, foaming agent and the reaction of other isocyanates and non-reactive component mixing Object constitutes second component, commonly known as component in terms of " B- ".Correspondingly, polyurethane or polyisocyanurate foam are easy to logical Following manner is crossed to prepare: the component in terms of A- and B- is brought together, convergence is by hand mix (for small-sized system It is standby) and, it is preferable that one of machine-mixing techniques are carried out to form block, plate, and laminate topples over panel and other objects in situ Part, the foam being spray applied, bubble, and the like.
It has been found, however, that two-component system has composition in terms of reduced B-, (especially those use certain hydrogen halogen For the system of alkene such as HFO-1234ze and HCFO-1233zd) shelf-life.In general, when a kind of foam is by by A and B The component of aspect bring together and generate when, a kind of good foam will be obtained.However, if with polyisocyanates By the polyol pre-mix composition aging before being handled, then these foams are that have lower quality and even exist It may collapse in the forming process of the foam.The foaming structure of the difference is attributed to certain catalyst and certain hydrogen alkenyl halides The reaction of (including HFO-1234ze and HCFO-1233zd), the reaction cause the foaming agent decomposed and, subsequently, The undesirable modification of these polymer organic silicon surface active agents.
Overcome a kind of mode of this problem, for example, be by the way that foaming agent, surfactant and catalyst are separated, And using it is a kind of with " A- " or " B- " for the use of the stream separated of component guide them.However, a kind of preferred solution party Case will not require such make again or technique change.A kind of preferable method can be using a kind of catalyst, the catalysis Agent has lower reactivity to certain foaming agents.The catalyst for being usually used in polyurethane chemistry can be divided into two wide kinds Class: amine compounds and metal-organic complex.Whether they, which push, generally is based on to the selection of amine catalyst: the gel Catalysis (or polymerization) reaction, wherein polyfunctional isocyanate and polyol reaction are to form polyurethane；Or the foaming promoter (or produce Angry body) reaction, wherein the isocyanates is reacted with water to form polyureas and carbon dioxide.Amine catalyst can also push isocyanide Acid esters trimerization reaction.It is usual to their selection since some amine catalysts will push all three kinds to react to a certain degree Be be conducive to based on them a kind of reaction be more than it is another how much.Since currently known certain amine catalysts foam to alkenyl halide Agent has a detrimental effect, a kind of stable polyol pre-mix composition be it is desired, the composition will reduce or eliminate Such unfavorable interaction.In addition, a kind of method for stablizing thermosetting foams blend, resulting stable premix Close object blend preparation and environmental-friendly polyurethane or polyisocyanurate foam with good foaming structure still So it is highly desirable to.
Invention summary
It has now been discovered that metal salt can play the polyol pre-mix combination stablized comprising catalyst and foaming agent The effect of object.Specifically, it has now been found that metal salt may be advantageously used with stable a kind of comprising halocarbon alkene foaming agent Polyol pre-mix B in terms of.Pass through it was found that this antihunt means extend the shelf-life of the premix and enhance Combine the polyol pre-mix composition with a kind of polyisocyanates the foam characteristics of the foam obtained.
Therefore, these polyol pre-mix compositions for including metal salt are the advantageous of traditional polyol pre-mix Substitute, find these traditional polyol pre-mix in the catalyst (such as a kind of amine catalyst) and the halocarbon alkene There is negative interaction between hydrocarbon.In the case where being not limited to any theory, these metal salts are considered as protecting the surface-active Agent protects it from a kind of nucleophillic attack of the catalyst (such as amine catalyst), and it is clear to can function as sour (such as hydrofluoric acid) Except agent.It is steeped in the method for stablizing thermosetting foams blend, and in the polyurethane or poly-isocyanurate of the acquisition In foam, these metal salts may be used as a kind of stabilization component of polyol pre-mix blend.It was found that method of the invention goes out The polyol pre-mix composition is stabilized to people's will material, thus the longer shelf-life is provided.That is, according to the present invention polynary Alcohol premix composition can be stored the time cycle of lasting length and have seldom to their feature or characteristic or not have Detrimental effect.It was found that by making polyol pre-mix composition and the A aspect component comprising polyisocyanates of the invention React generation foam have enhancing foam characteristics and can be used to meet low or zero ozone depletion potential, more Low global warming potential, the demand of low VOC content and low toxicity, so that they are environmental-friendly.
In one embodiment, the present invention provides a kind of polyol pre-mix composition, the premix compositions Including a kind of foaming agent, a kind of polyalcohol, a kind of surfactant, a kind of carbon monoxide-olefin polymeric and a kind of metal salt.This is urged Agent composition may include a kind of amine catalyst or non-amine catalyst.The foaming agent may include a kind of halogenated hydrogen alkene With, optionally, hydro fluorocarbons (HFC), hydrofluoroether class (HFE), hydro carbons, alcohols, aldehydes, ketone, ethers/bis- ethers, esters or Generate CO2Material or their combination.The surfactant can be a kind of organosilicon or non-organic silicon surfactant. In another embodiment, the present invention provides a kind of for generating two parts system of thermosetting foams blend, and wherein this is System includes: (a) as a first part, a kind of polyisocyanates and, optionally, the compatible original of one or more isocyanates Material；And it (b) is used as a second part, a kind of polyol pre-mix composition, the premix composition includes one kind Foaming agent, a kind of polyalcohol, a kind of surfactant, a kind of carbon monoxide-olefin polymeric and a kind of metal salt.The catalyst combination Object may include a kind of amine catalyst or non-amine catalyst.
In an other embodiment, the present invention is a kind of method for generating thermosetting foams blend, the party Method includes being combined the following terms: (a) a kind of polyisocyanates and, optionally, one or more isocyanates are compatible Raw material；And a kind of (b) polyol pre-mix composition, which includes a kind of foaming agent, a kind of polynary Alcohol, a kind of surfactant, a kind of carbon monoxide-olefin polymeric and a kind of metal salt.The carbon monoxide-olefin polymeric may include one kind Amine catalyst or non-amine catalyst.In another embodiment, the present invention provides a kind of mixture, which is suitable for mentioning Seldom or the pore structure without foam collapses polyurethane or poly- chlorinated isocyanurates foam are had with uniform for a kind of, Wherein the mixture include: a kind of (a) polyisocyanates and, optionally, the compatible raw material of one or more isocyanates；And (b) a kind of polyol pre-mix composition, the premix composition include a kind of foaming agent, a kind of polyalcohol, Yi Zhongbiao Face activating agent, a kind of carbon monoxide-olefin polymeric and a kind of metal salt.The carbon monoxide-olefin polymeric may include a kind of amine catalyst or Non- amine catalyst.Correspondingly, polyurethane or polyisocyanurate foam are easy in the following manner to prepare: by A- and the side B- The component in face is brought together, convergence be by hand mix (for small-sized preparation) and, it is preferable that one of machine-mixing techniques It carries out to form block, plate, laminate topples over (pour-in-place) panel and other objects, the bubble being spray applied in situ Foam, bubble (froth), and the like.
Have discovered unexpectedly that metal salt is unfavorable anti-between traditional catalyst and hydrogen alkenyl halide by offsetting Answering property and play the role of stable polyol pre-mix composition.Make in a kind of polyol pre-mix blend composition A kind of thermoset blend composition is unexpectedly produced with one or more metal salts, which, which has, changes Kind shelf life stability.These metal salts can be metal carboxylate, metal acetylacetonates, metal alcoholate, for example, Alkaline earth metal carboxylation, alkaline-earth metal acetylacetonate and alcoholates, alkali metal carboxylate, alkali metal acetylacetonate and Alcoholates and the carboxylate of the following terms, acetylacetonate and alcoholates: zinc (Zn), cobalt (Co), tin (Sn), cerium (Ce), Lanthanum (La), aluminium (Al), vanadium (V), manganese (Mn), copper (Cu), nickel (Ni), iron (Fe), titanium (Ti), zirconium (Zr), chromium (Cr), scandium (Sc), Calcium (Ca), magnesium (Mg), strontium (Sr) and barium (Ba), bismuth (Bi).These carboxylates, acetylacetonate and alcoholates can be held It changes places and is configured to a kind of typical polyol pre-mix.Specifically, any metal carboxylic with one or more functions group Hydrochlorate, acetylacetonate and alcoholates can use in catalyst of the invention.Such metal carboxylate, levulinic Ketonates and alcoholates may include, for example, magnesium formate, magnesium benzoate, magnesium octoate, calcium formate, calcium octoate, zinc octoate, octanoic acid Cobalt and stannous octoate, zinc acetylacetonate, acetylacetonate cobalt, acetylacetonate magnesium, calcium acetylacetonate.Optionally, may be used It is used for and the polyol pre-mix with being used to dissolve those for a kind of solvent such as ethylene glycol, diethylene glycol and toluene The metal salt that composition is mixed.In addition, unexpected and unexpectedly by by a kind of polyalcohol of the invention These foams that premix composition and a kind of polyisocyanates are blended to produce have it is a kind of uniformly with seldom or Without the pore structure of foam collapses.
The detailed description of certain embodiments of the present invention
By using chloro- 3,3,3- trifluoro propene (the commonly known as HCFO- of alkenyl halide such as hydro-chloro fluoroolefin 1- 1233zd) study polyurethane foam.Blend for polyurethane foam include a kind of polyalcohol, a kind of surfactant, A kind of amine catalyst, a kind of halogenated olefin blowing agents and a kind of metal salt.It has now been surprisingly discovered that making in the present invention The metal salt leads to the improved stability of these foamed blends over time.Furthermore, it was thus unexpectedly found that this The foam obtained a bit has a kind of uniformly with pore structures seldom or without foam collapses.
In the case where being not limited to the theory, it is believed that these two-component systems are (especially with that of HCFO-1233zd Reduced shelf life stability problem a bit) has with the alkenyl halide and a kind of reacting for the catalyst (such as amine catalyst) It closes.The reaction produces hydrofluoric acid (HF), which corrodes the organic silicon surfactant in situ.This side reaction is by hydrogen , fluorine and nuclear magnetic resonance (NMR) spectrum and gas chromatography-mass spectrography (GC-MS) of silicon confirmed.This effect can To be summarized as the catalyst (such as a kind of amine catalyst) to the C of the HCFO-1233zd alkenyl halide1Nucleophillic attack.Therefore, The embodiment of the present invention by reduce the reactivity of the HCFO-1233zd alkenyl halide and the catalyst reduce it is such not The interaction of benefit.Be not limited to it is any theory in the case where, it is believed that the reduction of the degradation of the alkene as caused by the catalyst with These metal salts play the role of protecting the halogenated olefin blowing agents related.This defencive function of these metal salts prevents this The unfavorable interaction of the HF product of catalyst and alkenyl halide such as HCFO-1233zd and the acquisition.These metal salts It is also used as working for the scavenger of hydrofluoric acid.In this way, these metal salts " removing " are any by the haloalkene The HF for reacting (such as reaction by using a kind of amine catalyst) generation of hydrocarbon and the catalyst.
Ladies and gentlemen inventor of the invention is it has now been discovered that metal salt, for example, metal carboxylate, metal acetylacetonate Object, metal alcoholate, as alkaline earth metal carboxylation, alkaline-earth metal acetylacetonate and alcoholates, alkali metal carboxylate, alkali Metal acetylacetonates and alcoholates and the carboxylate of the following terms, acetylacetonate and alcoholates: zinc (Zn), cobalt (Co), tin (Sn), cerium (Ce), lanthanum (La), aluminium (Al), vanadium (V), manganese (Mn), copper (Cu), nickel (Ni), iron (Fe), titanium (Ti), zirconium (Zr), chromium (Cr), scandium (Sc), calcium (Ca), magnesium (Mg), strontium (Sr) and barium (Ba), bismuth (Bi) have good hydrofluoric acid (HF) clear Except agent activity and play the role of stablizing the polyol blends.It is, for example, possible to use with one or more functions The metal carboxylate of carboxylic group.The metal carboxylate may include a kind of metal salt of C1-C21 carboxylic acid.For example, the metal carboxylic Hydrochlorate may include a kind of metal salt of C1-C21 linear chain or branched chain Aliphatic monoacid.Similarly, a kind of metal can be used Alcoholates for example, as a kind of metal salt including C1-C21 alcohol metal alcoholate.The metal alcoholate may include a kind of C1- The metal salt of C21 linear chain or branched chain fatty alcohol.Suitable carboxylic acid includes, but are not limited to formic acid, octanoic acid, 2 ethyl hexanoic acid etc..It is suitable The alcohol of conjunction includes methanol, ethyl alcohol, isopropanol etc..In one embodiment, which includes a kind of carboxylate of metal, The metal is selected from the group being made of Zn, Co, Ca and Mg.Suitable metal carboxylate may include, for example, magnesium formate, benzoic acid Magnesium, magnesium octoate, calcium formate, calcium octoate, zinc octoate, cobalt octoate, stannous octoate, zinc acetylacetonate, acetylacetonate cobalt, acetyl Acetonation magnesium and calcium acetylacetonate.
On the whole, it has used the amount to the effective one or more metal salts of the following terms: having improved polyalcohol premix The stability of polymer composition is more than the stabilization observed in same composition in the case where any metal salt is not present Property, and/or such as compared with the quality, froth obtained in the case where any metal salt is not present, improve by the way that the polyalcohol is pre- The quality of foam for being combined and obtaining in terms of blend composition and a kind of A for being made of polyisocyanates.Such amount Can according to a kind of specific preparation details and change, these details include, such as the type of the following terms And amount: foaming agent, catalyst and the surfactant used and this or these specific metal salts of selection, but this The amount of sample can be determined easily by routine experiment.However typically, based on the gross weight of the polyol pre-mix composition Amount, the amount of by weight at least about 0.1% or at least about 0.3% metal salt will be suitable.On the whole, it is not necessary that Using the total weight based on the polyol pre-mix composition, by weight greater than about 10% or about 5% metal salt contains Amount.For example, total weight of the polyol pre-mix composition based on the polyol pre-mix composition may be comprising by weight Meter about 0.1% to about 10% or the metal salt of by weight about 0.3% to about 5%.For example, can be by this or these metals The other components in drying or solution form of salt and the premix composition are combined.
Present invention accordingly provides a kind of polyol pre-mix composition, which includes a kind of foaming Agent, a kind of polyalcohol, a kind of surfactant, a kind of carbon monoxide-olefin polymeric and a kind of metal salt.The carbon monoxide-olefin polymeric can To include a kind of amine catalyst or a kind of non-amine catalyst.In another embodiment, the present invention provides a kind of stable heat Solidity foamed blend, the foamed blend include: a kind of (a) polyisocyanates and, optionally, a variety of isocyanates are compatible Raw material；And a kind of (b) polyol pre-mix composition, which includes a kind of foaming agent, a kind of polynary Alcohol, a kind of surfactant, a kind of carbon monoxide-olefin polymeric and a kind of metal salt.The carbon monoxide-olefin polymeric may include one kind Amine catalyst or a kind of non-amine catalyst.In another embodiment, the present invention is a kind of total for stablizing thermosetting foams The method of mixed object, this method include being combined the following terms: (a) a kind of polyisocyanates and, optionally, a variety of isocyanic acids The compatible raw material of ester；And a kind of (b) polyol pre-mix composition, the premix composition include a kind of foaming agent, A kind of polyalcohol, a kind of surfactant, a kind of carbon monoxide-olefin polymeric and a kind of metal salt.The carbon monoxide-olefin polymeric can be with Including a kind of amine catalyst or a kind of non-amine catalyst.A kind of stable blister is produced according to the mixture of this method Thermoset composition, the thermoset composition can be used for being formed polyurethane or polyisocyanurate foam.
Metal salt of the invention can be used in the polyol pre-mix composition comprising a variety of amine catalysts.Tradition Amine catalyst be tertiary amine, such as triethylenediamine (TEDA), dimethyl cyclohexyl amine (DMCHA) and dimethyl ethanol Amine (DMEA).Whether they, which push gelling reaction or foamable reaction, generally is based on for the selection of amine catalyst.In the glue In solidifying reaction, polyfunctional isocyanates and polyol reaction are to form polyurethane.In the foamable reaction, the isocyanates with Water is reacted to form polyureas and carbon dioxide.Amine catalyst can also push isocyanate trimerization to react.These reactions are with difference Speed carry out；The two react equal speed depending on temperature, levels of catalysts, catalyst type and various other factors. However, the gelling reaction of competition and the speed of foamable reaction must be appropriate balances in order to generate the foam of high-quality.If The foamable reaction occurs faster than the gelling reaction, and the gas generated by the reaction may be sufficiently strong to accommodate in the polymer It is expanded before it and internal division or foam collapses may occur.In contrast, if the gelling reaction is than the foamable reaction Occur faster, these foam holes will remain closed, so as to cause when it cool down when, the foam contraction.Molecular structure urges this The intensity and selectivity of agent give some hints.Generally there is kicker one to be separated by two carbon atoms with tertiary carbon Ehter bond.Strong gel catalyst may include alkyl-substituted nitrogen, and weaker gel catalyst may include it is cyclosubstituted Nitrogen.Catalyst for trimerization may include the triazine structure or quaternary ammonium salt.It can also use comprising a hydroxyl group or a work The catalyst of property amino hydrogen.
As described above, catalyst plays a part of to control and balances the gelling reaction and foamable reaction.Tertiary amine catalyst tool There are the special catalytic characteristics of themselves to be for example gelled, foaming and crosslinking active.Such as there is by this field the people of ordinary skill Member it will be understood that, the initiation indicatrix (rise profile) of these catalyst activities and resulting foam, bubbling efficiency, Moldability, productivity and other characteristics have strong relationship.Therefore, polyol pre-mix composition of the invention It further include metal salt other than a variety of amine catalysts to balance the foamable reaction, gelling reaction and catalyst for trimerization reaction And generate a kind of foam with desired characteristic.For example, polyol pre-mix composition of the invention may include With one or more metal salts of one or more oxygen containing amine catalyst combinations.Polyol pre-mix composition of the invention can Alternatively or additionally to include one or more non-oxygen containing amine catalysts and/or non-amine catalyst.
The oxygen-containing amine catalyst that can be used in the present invention includes containing those of ether and/or a hydroxyl group amine. For example, the oxygen-containing amine catalyst can be a catalyst such as N- alkyl for a kind of hydramine, ether amines or a kind of group containing morpholine Substituted morpholine.This catalyst may include the one, two, three or more nitrogen-atoms in amine functional group form. In one embodiment, all amine groups being present in the catalyst molecule are all tertiary amine groups.In one embodiment, This catalyst may include two, three or more oxygen atom, these oxygen atoms can be with ether group, hydroxyl group or ether The form of both group and hydroxyl group exists.Suitable oxygen-containing amine catalyst includes the chemical combination corresponding to following chemical structure Object:
R1R2N(CH2)2X(CH2)2Y
Wherein R1And R2It is same or different and an individually C1-C6Alkyl group, such as methyl and/or one A alkanol groups, such as-CH2CH2OH or CH2CH(CH3)OH；X is O, OH or NR3, wherein R3It is a C1-C6Alkyl base Group, such as methyl or an alkanol groups, such as-CH2CH2OH or CH2CH(CH3)OH；And Y is OH or NR4R5, wherein R4And R5It is same or different and an individually C1-C6Alkyl group, such as methyl and/or a chain triacontanol base Group, such as-CH2CH2OH or-CH2CH(CH3)OH；It includes at least one ether and/or hydroxyl that this, which obeys the following conditions i.e. compound, Base group.
Exemplary oxygen-containing amine catalyst includes:
Two-(2- dimethyl aminoethyl) ethers；
N, N- dimethylethanolamine；
N-ethylmorpholine；
N-methylmorpholine；
N, N, N '-trimethyl-N '-ethoxy-diamino ether；
N- (3- dimethylaminopropyl)-N, N- diisopropanolamine (DIPA)；
N, N- bis- (3- dimethylaminopropyl)-N- isopropanolamine；
2- (2- dimethylamino ethoxy) ethyl alcohol；
N, N, N '-trimethylammonioethyl-ethanol amine；And
2,2 '-dimorpholino diethyl ethers and its mixture.
Exemplary amines catalyst includes: N- (3- dimethylaminopropyl)-N, N- diisopropanolamine (DIPA), N, (the 3- diformazan of N- bis- Base aminopropyl)-N- isopropanolamine, 1,3- propane diamine, N '-(3- dimethylamino) propyl-N, N- dimethyl-, triethylene Diamines, DMIZ 1,2 dimethylimidazole, 1,3- propane diamine, N '-(3- (dimethylamino) propyl)-N, N- dimethyl-, N, N, N ' N '- 4-methyl hexamethylene diamine, N, N ", N "-trimethylaminoethyl group piperazine, 1- methyl -4- (2- dimethyl aminoethyl) piperazine, N, N, N ', N '-tetramethylethylenediamine, N, N- dimethyl cyclohexyl amine (DMCHA), two-(N, N- dimethyl aminoethyl) ethers (BDMAFE), Two ring of 1,4- diazonium [2,2,2] octane (DABCO), 2- ((2- dimethylamino ethoxy)-ethyl-methyl-amino) ethyl alcohol, 1- (two (3- dimethylamino)-propyl) amino -2- propyl alcohol, N, N ', N "-three (3- dimethylammo-propyl) Hexahydrotriazine, 1,3, 5- tri- (3- (dimethylamino) propyl-hexahydro-s- triazine, dimorpholino diethyl ether (DMDEE), N, N- dimethyl benzylamine, N, N, N ', N ", N "-pentamethyldipropylenetriamine, N, N '-diethyl piperazine, dicyclohexylmethylamine, ethyl diisopropylamine, diformazan Basic ring hexylamine, dimethylisopropylamine, isopropyl methyl benzylamine, methylcyclopentyl benzylamine, isopropyl-sec-butyl-trifluoroethylamine, two Ethyl-(α-phenethyl) amine, Tri-n-Propylamine, dicyclohexyl amine, tert-butyl isopropylamine, two tert-butylamines, cyclohexyl-tert-butylamine, di-secondary Butylamine, two cyclopentamines, two-(α-trifluoromethyl ethyl) amine, two-(α-phenethyl) amine, trityl amine and 1,1- diethyl Base-n-propylamine.Other amine include morpholine, imidazoles, the compound containing ether, for example, dimorpholino diethyl ether, N-ethylmorpholine, N-methylmorpholine, two (dimethyl aminoethyl) ethers, imidazoles (imidizole), n- methylimidazole, DMIZ 1,2 dimethylimidazole, two Morpholino dimethyl ether, N, N, N ', N ', N ", N "-pentamethyldipropylenetriamine and two (diethylamino ethyl) ethers, two (dimethylaminopropyl) ether, lupetazin, diethyl amino propylamine, ethyl amido alcohol, DEAE diethylaminoethanol, isopropyl Base ethylaminoethanol, butylamino ethyl alcohol, DBAE dibutylamino ethanol, butyl diethanolamine, t-butylaminoethyl, diethyl hydroxyl Amine and their combination.
Exemplary non-amine catalyst includes the organo-metallic compound containing the following terms: bismuth, lead, tin, antimony, cadmium, cobalt, Iron, thorium, aluminium, mercury, zinc, nickel, cerium, molybdenum, titanium, vanadium, copper, manganese, zirconium, magnesium, calcium, sodium, potassium, lithium or their combination such as octanoic acid are sub- Tin, dibutyl tin dilaurate (DGTDL), dibutyltin mercaptide, phenyl mercury propionate, lead octoate, potassium acetate/potassium octanoate, acetic acid Magnesium, oxalic acid titanyl, oxalic acid titanyl potassium, formic acid quaternary ammonium and acetylacetonate iron and their combination.
Due to the processing to mercury and lead catalyst and the material of catalysis (such as in the harmful waste in the U.S.) toxicity and must The property wanted can more advantageously use bismuth carboxylate salt and zinc carboxylate prior to the catalyst based on mercury and lead, however, these salt can It can be had the disadvantage in working life and in certain weather conditions or application.Alkyl tin carboxylate, oxide and mercaptides object For in the application of all types of polyurethane.Organo-metallic catalyst is useful in two-part polyurethane system.It is different with this Cyanate-water reaction is compared, these catalyst are designed to be directed towards isocyanate-hydroxyl reaction height selection, thus It avoids generating bubble under low humidity level.
It such as will be understood that by those of ordinary skill in the art, based on different factors such as temperature, Ke Yixuan These catalyst of the invention are selected to generate the gelling reaction speed and foamable reaction speed of balance.The reaction for competing both Balance will generate the foaming structure of high-quality.One common skilled craftsman is further understood that, can individually or with it is organic Metal catalyst combinations realize the desired function of resulting foaming structure using these catalyst of the invention together Characteristic and feature.This includes, but are not limited to other with gelling reaction functionality or the functional catalyst of foamable reaction.
The foaming agent in the thermosetting foams blend includes a kind of unsaturated in one embodiment of the invention For example a kind of HF hydrocarbon (HFO) of halogenated hydrogen alkene, hydro-chloro fluoroolefin (HCFO) or their mixture and optionally One or more hydro fluorocarbons (HFC), hydrofluoroether class (HFE), hydro carbons, alcohols, aldehydes, ketone, ethers/bis- ethers or generation two The material of carbonoxide.Preferred foaming agent is individual or in combination in the thermosetting foams blend of the invention A kind of HF hydrocarbon (HFO) or a kind of hydro-chloro fluoroolefin (HCFO).Preferred HF hydrocarbon (HFO) foaming agent include 3,4,5 or 6 carbon and including but not limited to pentafluoropropene, such as 1,2,3,3,3- pentafluoropropenes (HFO 1225ye)；Tetrafluoropropene, example Such as 1,3,3,3- tetrafluoropropenes (HFO 1234ze, E and Z isomers), 2,3,3,3- tetrafluoropropenes (HFO 1234yf), and 1,2,3,3- tetrafluoropropene (HFO1234ye)；Trifluoro propene, such as 3,3,3- trifluoro propenes (1243zf)；Tetrafluoro butylene, such as (HFO 1345)；Five fluorine butylene isomers, such as (HFO1354)；Hexafluorobutene isomers, such as (HFO1336)；Seven fluorine butylene Isomers, such as (HFO1327)；Seven fluorine pentene isomers, such as (HFO1447)；Octafluoro pentene isomers, such as (HFO1438)；Nonafluoropentene isomers, such as (HFO1429)；And hydro-chloro fluoroolefin, such as 1- chloro-3,3,3 ,-trifluoropropene (HCFO-1233zd) (E and Z isomers), 2- chloro-3,3,3 ,-trifluoropropene (HCFO-1233xf), HCFO1223,1,2- bis- is chloro- 1,2- difluoroethylene (E and Z isomers), 3,3- bis- chloro- 3- fluoropropenes, 2- chloro- 1,1, Isosorbide-5-Nitrae, (E and Z are different for 4,4- hexafluorobutenes -2 Structure body) and chloro- 1,1,1,3,4,4,4- seven fluorine butene-2 (E and Z isomers) of 2-.It is total in the thermosetting foams of the invention Preferred foaming agent includes the unsaturated halogenated hydrogen alkene with the normal boiling point less than about 60 DEG C in mixed object.Preferred hydrogen Chlorine fluoroolefins foaming agent includes, but are not limited to 1- chloro-3,3,3 ,-trifluoropropene；E and/or Z1233zd；1,3,3,3- tetrafluoro third Alkene；And E and/or Z 1234ze.
These can be used in thermosetting foams blend of the invention individually or together with other blowing agent combinations Halogenated olefin blowing agents, these other foaming agents include but is not limited to:
(a) hydro fluorocarbons, these hydrofluoroalkanes include but is not limited to difluoromethane (HFC32)；1,1,1,2,2- pentafluoroethane (HFC125)；1,1,1- trifluoroethane (HFC143a)；1,1,2,2- tetrafluoroethane (HFC134)；1,1,1,2- tetrafluoroethane (HFC134a)；1,1- Difluoroethane (HFC152a)；1,1,1,2,3,3,3- heptafluoro-propane (HFC227ea)；1,1,1,3,3- five Fluoro-propane (HFC245fa)；Ten fluorine penta of 1,1,1,3,3-pentafluorobutane (HFC365mfc) and 1,1,1,2,2,3,4,5,5,5- Alkane (HFC4310mee),
(b) hydro carbons, these hydrocarbon include but is not limited to pentane isomers and butane isomers；
(c) hydrofluoroether class (HFE) is for example, C4F9OCH3(HFE-7100)、C4F9OC2H5(HFE-7200)、CF3CF2OCH3 (HFE-245cb2)、CF3CH2CHF2(HFE-245fa)、CF3CH2OCF3(HFE-236fa)、C3F7OCH3(HFE-7000), 2- tri- Ten difluoro hexane (HFE 7500) of methyl fluoride -3- ethyoxyl, 1,1,1,2,3- hexafluoro -4- (the third oxygen of 1,1,2,3,3,3- hexafluoro Base)-pentane (HFE-7600), fluoro- 3- methoxyl group -4- (trifluoromethyl) pentane (HFE- of 1,1,1,2,2,3,5,5,5- ten 7300), nine fluorine isobutyl ether of ethyl/ethyl no nafluoro butyl ether (HFE 8200), CHF2OCHF2、CHF2-OCH2F、CH2F- OCH2F、CH2F-O-CH3, ring-CF2CH2CF2- O, ring-CF2CF2CH2-O、CHF2-CF2CHF2、CF3CF2-OCH2F、CHF2-O- CHFCF3、CHF2-OCF2CHF2、CH2F-O-CF2CHF2、CF3-O-CF2CH3、CHF2CHF-O-CHF2、CF3-O-CHFCH2F、 CF3CHF-O-CH2F、CF3-O-CH2CHF2、CHF2-O-CH2CF3、CH2FCF2-O-CH2F、CHF2-O-CF2CH3、CHF2CF2-O- CH3(HFE254pc)、CH2F-O-CHFCH2F、CHF2-CHF-O-CH2F、CF3-O-CHFCH3、CF3CHF-O-CH3、CHF2-O- CH2CHF2、CF3-O-CH2CH2F、CF3CH2-O-CH2F、CF2HCF2CF2-O-CH3、CF3CHFCF2-O-CH3、CHF2CF2CF2-O- CH3、CHF2CF2CH2-OCHF2、CF3CF2CH2-O-CH3、CHF2CF2-O-CH2CH3、(CF3)2CF-O-CH3、(CF3)2CH-O- CHF2(CF3)2CH-O-CH3And their mixture；And
(d) C1 to C5 alcohols, C1 to C4 aldehydes, C1 to C4 ketone, C1 to C4 ethers and two ethers and generation titanium dioxide The material of carbon.
Thermosetting foams blend of the invention includes that one or more be capable of forming has generally honeycomb structure Foam and one or more foaming agents.The example of thermoset composition includes polyurethane and polyisocyanurate foam combination Object, preferably low density foam, it is flexible or rigid.
The invention further relates to the foam prepared from thermosetting foams preparation, and preferred closed-cell foam, at this It joined the ester of a stable quantity in preparation.When using a kind of ester, is formed and/or be added in the composition that can be blistered The combined sequence and mode of foaming agent and ester of the invention generally will not influence operability of the invention.For example, poly- In the case where urethane foam, it is possible to the combined different component of the foaming agent and ester does not mix before introducing foaming machine, Or notably these components are added without the same position in the foaming machine.Therefore, in certain embodiments, desired can be with It is that one or more components i.e. these components of the combination for introducing the foaming agent and ester in such a will enter together The foaming machine.Nevertheless, in certain embodiments, combining the combined component of the foaming agent and ester in advance, and one Rise is introduced into this can be in Efferescent compositions (directly or as a kind of a part of premix), the premix and then further Be added this can Efferescent compositions other parts.
In certain embodiments, in the preparation of polyurethane polyol foam, polyol pre-mix composition in terms of the B It may include polyalcohol, the surfactant based on organosilicon or non-organic silicon, catalyst, fire retardant or suppressant, acid removing Agent, free radical scavenger, filler and other stabilizers or inhibitor.These catalyst may include a kind of amine catalysis Agent or a kind of non-amine catalyst.
The polyol component (may include polyol blends) can be any polyalcohol, and the polyalcohol is known to one kind Mode and a kind of isocyanates react during preparing a kind of polyurethane or polyisocyanurate foam.It is exemplary more First alcohol include: the polyether polyol based on glycerol for exampleGP-700,GP-725,GP-4000,GP-4520；It is based on The polyether polyol of amine is for exampleTEAP-265 and EDAP-770,AD-310；Polyethers based on sucrose Type polyhydric alcohols are such asSD-360, SG-361 and SD-522,490 andSPA-357；Base In Mannich (Mannich) polyether polyol for exampleR-425X and R-470X；Polyethers based on D-sorbite Type polyhydric alcohols are such asS-490；And aromatic polyester polyol is for example2541 and 3510,PS-2352 andTR-925。
The polyol pre-mix composition can also include a kind of surfactant.The surfactant is used for from this It is a kind of with desired hole knot to obtain that the size of a kind of foam and the bubble for controlling the foam is formed in mixture The foam of structure.Preferably, it is desirable to a kind of wherein foam of the vesicle with uniform-dimension or unit, because it has most Desired physical characteristic such as compressive strength and thermal coefficient.Furthermore, it is critical that obtain a kind of foam, which, which has, stablizes , the unit that will not collapse before blistering or during foam is initiated.For in polyurethane or polyisocyanurate foam preparation Used in organic silicon surfactant be obtained by multiple trade names known to persons of ordinary skill in the art.It has sent out Existing such material be within the scope of large-scale preparation it is applicable, these preparations allow uniform unit formed and Maximum gas retains the foaming structure to realize very low-density.
Exemplary silicone surfactant includes polysiloxane polyoxyalkylene block copolymer for example from high moral Schmitt B8404, B8407, B8409, B8462 and B8465 obtained by company (Goldschmidt)；From Air Products Company (Air Products DC-193, DC-197, DC-5582 and DC-5598 obtained by)；It can get from Mai Tu company (Momentive) L-5130, L5180, L-5340, L-5440, L-6100, L-6900, L-6980 and L6988.Exemplary non-organic silicon surface Activating agent include sulfonate, the alkali metal salt of fatty acid, the ammonium salt of fatty acid, oleic acid, stearic acid, dodecylbenzene disulfonic acid, Dinaphthylmethanedisulfonic acid, ricinoleic acid, ethoxylated alkylphenol, ethoxylized fatty alcohol, paraffin oil, conticaster grease (caster oil ester), ricinoleate ester, turkey red oil, peanut oil, paraffin fatty alcohol or their combination.Surface The level that typically uses of activating agent is the about 0.4wt% to 6wt% from polyol pre-mix, and preferably from about 0.8wt% is extremely 4.5wt%, and more preferably from about 1wt% to 3wt%.
Example sex flame retardant includes trichloropropyl phosphate (TCPP), triethyl phosphate (TEP), diethyl ethyl phosphonic acid ester (DEEP), diethyl two (2- ethoxy) aminomethylphosphonic acid ester, the ester based on bromination acid anhydrides, two bromo neopentyl glycols, bromination Polyether polyol, melamine, ammonium polyphosphate, aluminium trihydrate (ATH), three (bis- chloro isopropyl of 1,3-) phosphates, three (2- Chloroethyl) phosphate, three (2- chloro isopropyl) phosphates, chlorine alkyl phosphate/oligomeric phosphonate, oligomeric chloroformate alkyl phosphate, Brominated flame retardant, dimethyl methylphosphonate, diethyl N, N bis- (2- ethoxy) aminomethylphosphonic acid based on penta-BDE Ester, oligomeric phosphonate and their derivative.
It in certain embodiments, include that acid scavenger, free radical scavenger, and/or others are steady in the premix Determine agent/inhibitor.Exemplary stabilizing agents/inhibitor includes 1,2- epoxy butane；Glycidol methyl ether；Cyclic terpene alkene such as cinene Alkene, Zuo Xuan limonene, You Xuan limonene；1,2- epoxy -2,2- methylpropane；Nitromethane；Diethylhydroxylamine；Alpha-Methyl benzene second Alkene；Isoprene；P-methoxyphenol；M- metoxyphenol；Xiao Xuan limonene oxide；Hydrazine；2,6- di-t-butyl phenol； Hydroquinone；Organic acids such as carboxylic acid, dicarboxylic acids, phosphonic acids, sulfonic acid, sulfamic acid, hydroxamic acid, formic acid, acetic acid, propionic acid, fourth Acid, caproic acid, isocaproic acid acid, 2 ethyl hexanoic acid, octanoic acid, cyanoacetic acid, pyruvic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, oneself Diacid, azelaic acid, trifluoroacetic acid, methanesulfonic acid, benzene sulfonic acid and their combination.It can also be including other additives for example Adhesion promotor, antioxidant, filler, hydrolysing agent, lubricant, antibacterial agent, pigment, viscosity modifier, resists antistatic agent UV agent.The example of these additives includes: sterically hindered phenol；Diphenylamines；Benzofuranone derivatives；Butylated Hydroxytoluene (BHT)；Carbon Sour calcium；Barium sulfate；Glass fibre；Carbon fiber；Microsphere；Silica；Melamine；Carbon black；Wax and soap；Antimony, copper and arsenic have Machine metal derivative；Titanium dioxide；Chromium oxide；Iron oxide；Glycol ether；Dimethyl AGS ester；Propylene carbonate；And hexichol Ketone and benzotriazole cpd.
In some embodiments of the invention, a kind of ester can be added in a kind of thermosetting foams blend.People out Find that a kind of addition of ester further improves the stability of the blend over time with expecting, such as this is pre- in extension The shelf-life of mixture, and enhance the characteristic aspect of the foam obtained.Ester useful in the present invention can have chemical formula R-C (O) (wherein R and R ' can be C to-O-R 'aHc-bGb, wherein G is a kind of halogen such as F, Cl, Br, I, and a=0 to 15, b=0 are extremely 31 and c=1 is to 31), and including being the ester of the product obtained by the esterification of the following terms: dicarboxylic acids, phosphinic acids, phosphine Acid, sulfonic acid, sulfamic acid, hydroxamic acid or their combination.Preferred ester be by using a kind of alcohol (such as methanol, ethyl alcohol, Ethylene glycol, diethylene glycol, propyl alcohol, isopropanol, butanol, isobutanol, amylalcohol, isoamyl alcohol and their mixture)；With a kind of acid (such as formic acid, acetic acid, propionic acid, butyric acid, caproic acid, isocaproic acid, 2 ethyl hexanoic acid, octanoic acid, cyanoacetic acid, pyruvic acid, benzoic acid, Oxalic acid, trifluoroacetic acid, oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, trifluoroacetic acid, methanesulfonic acid, benzene sulfonic acid and they Mixture) esterification obtain product.Preferred ester be allyl hexanoate, benzyl acetate, benzyl formate, Bronyl acetate, Butyl butyrate, ethyl acetate, ethyl butyrate, ethyl hexanoate, ethyl cinnamate, Ethyl formate, cognac oil, ethyl isovalerate, Ethyl lactate, ethyl pelargonate, ethyl valerate, geranyl acetate, geranyl butyrate, glutaconic nitrile, isobutyl acetate, formic acid are different Butyl ester, isoamyl acetate, isopropyl acetate, bergamio, linalyl butyrate, linalyl formate, methyl acetate, adjacent aminobenzene Methyl formate, methyl benzoate, methyl butyrate, methyl cinnamate, methyl formate, methyl valerate, methyl propionate, phenylacetic acid first Ester, gaultherolin, nonyl caprylate, octyl acetate, n-octyl butyrate, pentyl acetate/pentyl acetate (amyl acetate/ Pentyl acetate), amyl butyrate/amyl butyrate (pentyl butyrate/amyl butyrate), amyl caproate/oneself Sour pentyl ester (pentyl hexanoate/amyl caproate), amyl valerate/amyl valerate (pentyl pentanoate/ Amyl valerate), propyl acetate, propyl isobutyrate, the mixture of butyric acid terpenoid and they.Most preferred ester is formic acid Methyl esters, Ethyl formate, methyl acetate and ethyl acetate and their mixture.
The ester can be added together with the blowing agent combination by different means known in the art, or can To be added separately in the thermosetting foams blend with the foaming agent.A kind of typical amount of ester is total from thermosetting foams The about 0.1wt% to 10wt% of mixed object, a kind of preferred amount of ester be from the about 0.2wt% of thermosetting foams blend to 7wt%, and a kind of preferred amount of ester is the about 0.3wt% to 5wt% from thermosetting foams blend.
Prepare polyurethane using composition described herein or polyisocyanurate foam can imitate it is ripe in the art It is any in the method that can be used known, referring to Saunders and Frisch, I and II, polyurethane chemistry and technology are rolled up, 1962, John Wiley and Sons, New York, N.Y. or Gum, Reese, Ulrich, reaction polymer, 1992, Oxford University goes out Version, New York, N.Y. or Klempner and Sendijarevic, foam of polymers and foam technology, 2004, Hanser Gardner It publishes, Cincinnati, Ohio (see Saunders and Frisch, Volumes I and II Polyurethanes Chemistry and technology,1962,John Wiley and Sons,New York,N.Y.or Gum,Reese, Ulrich,Reaction Polymers,1992,Oxford University Press,New York,N.Y.or Klempner and Sendijarevic,Polymeric Foams and Foam Technology,2004,Hanser Gardner Publications,Cincinnati,Ohio).Generally, polyurethane or polyisocyanurate foam are to pass through group Unification kind of an isocyanates, the polyol pre-mix composition and for example optional fire retardant of other materials, colorant, Or other additives and prepare.These foams can be rigid, is flexible or semirigid, and can have one The mixture of kind hole-closing structure, a kind of open-celled structure or aperture and closed pore.
In numerous applications, it provides for polyurethane or polyisocyanurate foam in the preparation being blended in advance In these components be convenient.Most typically, which is to be blended into two kinds of components in advance.This isocyanates Optionally the compatible raw material of other a variety of isocyanates constitutes first component, commonly known as component in terms of " A- ".This is more First alcohol mixture composition, including surfactant, catalyst, foaming agent and optional other compositions constitute this second group Point, it is commonly referred to as component in terms of " B- ".In any given application, component can not include more than all in terms of being somebody's turn to do " B- " The component listed, if such as some preparations eliminate the foam characteristic that the fire retardant this feature is not a kind of requirement.Accordingly Ground, polyurethane or polyisocyanurate foam are easy in the following manner prepare: the component in terms of A- and B- is converged to one Rise, convergence be by hand mix (for small-sized preparation) and, it is preferable that one of machine-mixing techniques are carried out to form block, Plate, laminate topple over panel and other objects in situ, the foam being spray applied, bubble, and the like.It is optionally possible to Using other ingredients for example fire retardant, colorant, blowing promotor, water and even other polyalcohols as it is a kind of stream and add Add to the mixing head or reaction site.However, group divides it in terms of they most advantageously all to be mixed to a kind of B as described above In.In some cases, A and B can be prepared and is mixed into the component that one kind has wherein removed water.When to this one When first component mixture carries out blowing and is exposed to air, polymerization reaction occurs.For example, being steeped for one kind comprising a component Foam mixture is used for for the foam spray tank of simple application, this is typical.
A kind of composition to blister suitable for forming polyurethane or polyisocyanurate foam can be by making one kind Organic multiple isocyanate reacts to be formed with the above-mentioned polyol pre-mix composition.In polyurethane or poly-isocyanurate Any organic multiple isocyanate can be used including aliphatic or aromatic polyisocyanates in foam synthesis.It is suitble to Organic multiple isocyanate include aliphatic, alicyclic, fragrant fat subsitutes race, aromatic and heterocycle isocyanic acid Ester, these isocyanates are known in art of polyurethane chemistry.
Example
By further showing the present invention referring to these following examples.
Example 1
Example 1 is shown by using a kind of improved stabilization that metal salt (such as a kind of alkali salt of carboxylic acid) is given Property, which, which has good hydrofluoric acid (HF) scavenger activity and give the polyol pre-mix composition, stablizes Property.Magnesium formate has been used in this example, but can be with other metal salt (such as alkaline-earth metal used according to the invention Carboxylate, alkaline-earth metal acetylacetonate, alkali metal carboxylate, alkali metal acetylacetonate and the following terms carboxylic Hydrochlorate, acetylacetonate and alcoholates: zinc (Zn), cobalt (Co), tin (Sn), cerium (Ce), lanthanum (La), aluminium (Al), vanadium (V), manganese (Mn), copper (Cu), nickel (Ni), iron (Fe), titanium (Ti), zirconium (Zr), chromium (Cr), scandium (Sc), calcium (Ca), magnesium (Mg), strontium (Sr), barium (Ba) and bismuth (Bi)) to improve the stability of the polyol pre-mix composition.
A kind of aqueous preparation is prepared for by mixing the following terms: the pentamethyl diethylidene three of 2wt% Amine (PMDETA), 4wt% organic silicon surfactant (B 8465), the magnesium formate of 2wt% and Hydro-chloro fluoroolefin (HCFO) HCFO-1233zd " E " halogenated olefin blowing agents of 92wt%.In order to compare, by by the following terms It mixes and is prepared for a kind of solution without containing magnesium formate: the five methyl diethylentriamine (PMDETA) of 2wt%, 4wt% organic silicon surfactant (B 8465) and 94wt% hydro-chloro fluoroolefin (HCFO) HCFO-1233zd " E " halogenated olefin blowing agents.Then both mixtures are continued 15 in 50 DEG C of agings in a baking oven It.By each sample and a kind of Deuterated chloroform (CDCl3) solution of solvent mixed.Then these blends are divided To obtain the NMR spectra at 25 DEG C, these spectrum are in the Bruker DRX 500 (11.7T) for being equipped with 5mm TBI probe for analysis It is obtained on spectrometer.It can will be with the interaction between the HCFO-1233zd " E " and the amine and organic silicon surfactant Related a small amount of product is normalized to HCFO-1233zd " E " and therefore makes its quantization.This is outlined in following table 1 Kind comparison result.
A kind of comparison of preparation of the table 1. in the case where using and without using metal salt
As shown in table 1, magnesium formate can pass through hydro-chloro fluoroolefin (HCFO) HCFO-1233zd " E " halogenated olefin blowing agents Unfavorable interaction between the amine and the surfactant inhibits the formation of product.The display of example 1 metal salt (such as A kind of alkali salt of carboxylic acid) there is good hydrofluoric acid (HF) scavenger activity and improve the polyol pre-mix group Close the stability of object.
Example 2
Example 2 shows that one kind does not include the comparison B aspect premix preparation of metal salt.According in following table 2 Component in terms of comparison B is blended the formula shown in advance.Component includes a kind of aqueous blend of the following terms in terms of the B: more First alcohol (such as those of sold by Dow Chemical (Dow Chemical) with trade name Voranol 490, public affairs are stepped by Hensel (Huntsman) is taken charge of with those of trade name Jeffol R-425-X sale and by Si Taipan company (Stepan Company) Those of sold with trade name Stepanpol PS-2352)；Industry-goldschmidt chemical corporation (Evonik Industries- is created by winning Degussa) with trade nameThe organic silicon surfactant that B 8465 is sold；And amine catalyst, especially With trade name8 sell dimethyl cyclohexyl amines and with trade name5 pentamethyls two sold Ethylenetriamine, the two be all can be obtained from air chemical products Co., Ltd (Air Products and Chemicals, Inc.).Component further includes Antiblaze 80 in terms of the B, and one kind coming from the fire retardant of Rhodia (Rhodia) company.
The comparison preparation of 2. example 2 of table.
Component Total Wt%
Voranol 490 36.77
Jeffol R-425-X 22.06
Stepanol 2352 14.71
Polycat 5 0.33
Polycat 8 1.06
Tegostab B8465 1.51
Antiblaze 80 4.98
Water 1.57
E1233zd 17.01
It amounts to 100.00
In terms of A- aspect/B- 1.11
The preparation (the ISO index with 115) of test is comprising one kind by Huntsman Corporation with trade name Rubinate M The polymeric methylene diphenyl diisocyanate (MDI) of sale is as component in terms of A.In this example, mixed manually with one Clutch is by component in terms of component (a kind of polymeric methylene diphenyl diisocyanate (MDI)) in terms of A and B (a kind of polyalcohol, table Face activating agent, catalyst, foaming agent and additive blend) mixed, and assign it in a container with It is formed and a kind of freely initiates foam.Total blowing level is 23.0ml/g.Three samples are prepared according to above-mentioned formula and are made It the period and carries out aging in different times under different conditions: a not aged sample, one in environment temperature aging The sample for continuing 15 days and a sample for continuing 15 days in 50 DEG C of agings.Measure the characteristic such as emulsification time (cream time), gelling time (gel time) and tack-free time freely initiate density (FRD) and quality, froth, These characteristics are outlined in following table 3:
The characteristic of the preparation of the aging for the example 2 that table 3. measures.
*Due to the quality, froth of difference, cannot be measured.
As shown in table 3 above, made the polyol pre-mix composition preparation aging of example 2 to foam product Matter has detrimental effect.It was found that there is the detrimental effect increased to quality, froth in the sample that 50 DEG C of agings continue 15 days, this Indicate that both these catalyst and surfactant almost lose the whole of their functional characteristic.Thus, it is found that example 2 Compare shelf life stability and performance characteristic that preparation has difference.
Example 3
Example 3 shows a kind of exemplary preparation of the invention, wherein polyol pre-mix composition packet in terms of the B- A kind of cobalt octoate solution (25wt% is in a kind of organic solvent) for including 2.9wt% is used as a kind of metal salt stabilizers.This is pungent Sour cobalt metal salt solution is added in the preparation and according in example 2 above the step of measures it.? Resulting characteristic is outlined in following table 4:
The characteristic of the preparation of the aging for the example 3 that table 4. measures.
There is the polyol pre-mix preparation aging of example 3 also to quality, froth It influences.It was found that there is the influence increased to quality, froth in the sample that 50 DEG C of agings continue 15 days.However, containing cobalt octoate metal The sample of the aging of salt has small more influences to blistering catalytic action, because when compared with not aged sample, the cream It agent, gelling and freely initiates density and only slightly increases.
Example 4
Example 4 shows a kind of exemplary preparation of the invention, wherein polyol pre-mix composition packet in terms of the B- A kind of potassium octanoate of 2.9wt% is included as a kind of metal salt stabilizers.The potassium octanoate metal salt solution is added in the preparation And the step of according in example 2 above, measures it.Resulting characteristic is outlined in following table 5:
The characteristic of the preparation of the aging for the example 4 that table 5. measures.
*Due to the quality, froth of difference, cannot be measured.
Shown that the polyol pre-mix preparation aging of example 4 to quality, froth There is very big adverse effect.It was found that there is the adverse effect increased to quality, froth in the sample that 50 DEG C of agings continue 15 days, this Indicate that both these catalyst and foaming agent almost lose the whole of their functional characteristic.
Example 5
Example 5 shows a kind of exemplary preparation of the invention, wherein polyol pre-mix composition packet in terms of the B- A kind of zinc octoate solution of 2.9wt% is included as a kind of metal salt stabilizers.The preparation is added in the zinc octoate metal salt solution The step of in product and according in example 2 above, measures it.Resulting spy is outlined in following table 6 Property:
The characteristic of the preparation of the aging for the example 5 that table 6. measures.
As shown in table 6 above, made the polyol blends preparation aging of example 5 only small to quality, froth Influence.When preparation is compared compared with this, find the sample for continuing 15 days in 50 DEG C of agings to quality, froth and blistering Catalytic action has small more influences, as shown in emulsification and gelling time measurement result.The emulsification of the sample of the aging Only has slight increase compared with the not aged sample with gelling time, this indicates that the halogenated olefin blowing agents pass through zinc octoate The addition of metal salt stabilizers is protected.
Example 6
Example 6 shows a kind of exemplary preparation of the invention, and wherein polyol blends include 2.9wt% in terms of the B- A kind of sad magnesium solution (2 ethyl hexanoic acid salt) be used as a kind of metal salt stabilizers.The magnesium octoate metal salt solution is added should The step of in preparation and according in example 2 above, measures it.Gained is outlined in following table 7 Characteristic:
The characteristic of the preparation of the aging for the example 6 that table 7. measures.
* it due to the quality, froth of difference, cannot be measured.
As shown in table 7 above, the polyol blends preparation of the aging of example 6 shows have to quality, froth Detrimental effect.It was found that having the adverse effect increased to quality, froth in the sample that 50 DEG C of agings continue 15 days, this instruction should Foaming agent almost loses its all functional characteristics.
Example 7
Example 7 shows a kind of exemplary preparation of the invention, and wherein polyol blends include 2.9wt% in terms of the B- A kind of sad calcium solution (2 ethyl hexanoic acid salt) be used as a kind of metal salt stabilizers.The magnesium octoate metal salt solution is added should The step of in preparation and according in example 2 above, measures it.Gained is outlined in following table 8 Characteristic:
The characteristic of the preparation of the aging for the example 7 that table 8. measures.
As shown in table 8 above, the polyol blends preparation of the aging of example 7 shows have to quality, froth Less adverse effect.It was found that there are small more influences to quality, froth in the sample that 50 DEG C of agings continue 15 days, this instruction The halogenated olefin blowing agents are protected by the addition of stabilizer.
Example 1 uses magnesium formate as a kind of HF scavenger and stabilizer.Metal salt, for example, metal carboxylate, metal second Acyl acetone solvate, metal alcoholate, as alkaline earth metal carboxylation, alkaline-earth metal acetylacetonate and alcoholates, alkali metal carboxylic Hydrochlorate, alkali metal acetylacetonate and alcoholates and the carboxylate of the following terms, acetylacetonate and alcoholates: zinc (Zn), cobalt (Co), tin (Sn), cerium (Ce), lanthanum (La), aluminium (Al), vanadium (V), manganese (Mn), copper (Cu), nickel (Ni), iron (Fe), titanium (Ti), zirconium (Zr), chromium (Cr), scandium (Sc), calcium (Ca), magnesium (Mg), strontium (Sr) and barium (Ba), bismuth (Bi) have good hydrogen fluorine Sour (HF) scavenger activity and play the role of stablizing the polyol blends.It is, for example, possible to use have one or more The metal carboxylate of functional carboxylic group.The metal carboxylate may include a kind of metal salt of C1-C21 carboxylic acid.For example, The metal carboxylate may include a kind of metal salt of C1-C21 linear chain or branched chain Aliphatic monoacid.Similarly, it can be used A kind of metal alcoholate for example, as a kind of metal salt including C1-C21 alcohol metal alcoholate.The metal alcoholate can wrap Include a kind of metal salt of C1-C21 linear chain or branched chain fatty alcohol.Suitable carboxylic acid includes, but are not limited to formic acid, octanoic acid, 2- ethyl Caproic acid etc..Suitable alcohol includes methanol, ethyl alcohol, isopropanol etc..In one embodiment, which includes a kind of carboxylic of metal Hydrochlorate, the metal are selected from the group being made of Zn, Co, Ca and Mg.Suitable metal carboxylate may include, for example, magnesium formate, Magnesium benzoate, magnesium octoate, calcium formate, calcium octoate, zinc octoate, cobalt octoate, stannous octoate, zinc acetylacetonate, acetylacetonate Cobalt, acetylacetonate magnesium and calcium acetylacetonate.These metal salts can use in polyol blends, these are polynary Alcohol blend includes oxygen containing amine catalyst (as shown in example 1) or other amine catalysts (such as the institute in example 2-7 Show) or with non-amine catalyst.Although the certain of these metal salts play the role of better than others, and lack The polyol blends of such metal salt are compared, and all polyol blends preparations comprising metal salt of the invention are all Show the unfavorable interaction between better stability and smaller alkenyl halide and catalyst.
Although the present invention is shown and illustrated referring to specific embodiment herein, it is not intended to limit the invention to Shown in details.On the contrary, within the range and degree of the equivalent of the claims and without departing substantially from situation of the invention Different modifications can be made in detail down.

Claims (10)

1. a kind of polyol pre-mix composition, the composition includes a kind of foaming agent including halogenated hydrogen alkene, one kind Polyalcohol, a kind of ester with chemical formula R-C (O)-O-R ', a kind of surfactant, one kind are by non-oxygen containing amine catalyst group At carbon monoxide-olefin polymeric and a kind of metal salt, wherein the metal salt be selected from metal carboxylate, acetylacetonate and Alcoholates, wherein metal be selected from zinc, cobalt, tin, cerium, lanthanum, aluminium, vanadium, manganese, copper, nickel, iron, titanium, zirconium, chromium, scandium, calcium, magnesium, strontium, barium and Bismuth, wherein R and R ' is CaHc-bGb, wherein G is a kind of halogen selected from F, Cl, Br, I, a=0 to 15, b=0 to 31 and c= 1 to 31.
2. polyol pre-mix composition as described in claim 1, wherein the foaming agent extraly includes one or more Hydro fluorocarbons (HFC), hydrofluoroether class (HFE), hydro carbons, alcohols, aldehydes, ketone, ethers/bis- ethers generate CO2Material, Or their combination.
3. polyol pre-mix composition as described in claim 1, wherein the foaming agent includes a kind of halogen selected from the group below The hydrogen alkene in generation, the group consisting of: hydrofluoroolefin (HFO), hydrochlorofluoroolefins (HCFO) and their mixing Object and optionally one or more hydro fluorocarbons (HFC), hydrofluoroether class (HFE), hydro carbons, alcohols, aldehydes, ketone, ethers/ Two ethers, esters or the material for generating carbon dioxide.
4. polyol pre-mix composition as described in claim 1, wherein the surfactant includes a kind of polysiloxanes Polyalkylene block copolymers organic silicon surfactant.
5. polyol pre-mix composition as described in claim 1, wherein the premix composition is based on the polyalcohol The total weight of premix composition includes the metal salt of from 0.3 to 5 weight percent.
6. polyol pre-mix composition as described in claim 1, wherein the metal salt includes a kind of carboxylate of metal And/or alcoholates, the metal are selected from the group being made of Zn, Co, Ca and Mg.
7. polyol pre-mix composition as described in claim 1, wherein the metal salt include a kind of C1-C21 carboxylic acid or The carboxylate and/or alcoholates of alcohol.
8. polyol pre-mix composition as described in claim 1, wherein the metal salt include a kind of C1-C21 straight chain or The Aliphatic monoacid of branch or the carboxylate of monohydric alcohol and/or alcoholates.
9. polyol pre-mix composition as described in claim 1, wherein the metal salt is selected from and is made of the following terms Group: magnesium formate, zinc octoate, calcium octoate, cobalt octoate and magnesium octoate and their mixture.
10. polyol pre-mix composition as described in claim 1, wherein the metal salt is selected from and is made of the following terms Group: acetylacetonate magnesium, zinc acetylacetonate, calcium acetylacetonate, acetylacetonate cobalt and their mixture.
CN201610505288.7A 2011-04-15 2012-03-06 The improved stability of polyurethane polyol blend comprising halogenated olefin blowing agents Active CN106046411B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US201161475789P 2011-04-15 2011-04-15
US61/475,789 2011-04-15
CN201280012689.9A CN103415548B (en) 2011-04-15 2012-03-06 Improved stability of polyurethane polyol blends containing halogenated olefin blowing agent

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201280012689.9A Division CN103415548B (en) 2011-04-15 2012-03-06 Improved stability of polyurethane polyol blends containing halogenated olefin blowing agent

Publications (2)

Publication Number Publication Date
CN106046411A CN106046411A (en) 2016-10-26
CN106046411B true CN106046411B (en) 2019-02-26

Family

ID=47009633

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201610505288.7A Active CN106046411B (en) 2011-04-15 2012-03-06 The improved stability of polyurethane polyol blend comprising halogenated olefin blowing agents
CN201280012689.9A Active CN103415548B (en) 2011-04-15 2012-03-06 Improved stability of polyurethane polyol blends containing halogenated olefin blowing agent

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN201280012689.9A Active CN103415548B (en) 2011-04-15 2012-03-06 Improved stability of polyurethane polyol blends containing halogenated olefin blowing agent

Country Status (10)

Country Link
US (1) US20140051776A1 (en)
EP (1) EP2702088B1 (en)
JP (1) JP5890895B2 (en)
CN (2) CN106046411B (en)
BR (1) BR112013023136B1 (en)
CA (1) CA2829347C (en)
ES (1) ES2674330T3 (en)
MX (1) MX348762B (en)
PL (1) PL2702088T3 (en)
WO (1) WO2012141822A1 (en)

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4223814A3 (en) * 2013-02-26 2023-08-23 Honeywell International Inc. Polyurethane foam premixes containing halogenated olefin blowing agents and foams made from same
US20140275303A1 (en) * 2013-03-15 2014-09-18 Clayton Corporation Rodent resistant polyurethane foams
EP3984986A1 (en) 2015-05-21 2022-04-20 The Chemours Company FC, LLC Hydrofluorination of 1233xf to 244bb by sbf5
US10350617B1 (en) * 2016-02-12 2019-07-16 Konstantin Dragan Composition of and nozzle for spraying a single-component polyurethane foam
JP6951012B2 (en) * 2016-05-16 2021-10-20 積水ソフランウイズ株式会社 Polyol composition for rigid polyurethane foam and method for producing rigid polyurethane foam
US10815353B1 (en) 2016-06-03 2020-10-27 Konstantin Dragan Composition of and nozzle for spraying a single-component polyurethane foam
US10702876B2 (en) * 2016-06-03 2020-07-07 Konstantin Dragan System, composition, and method for dispensing a sprayable foamable product
KR102433944B1 (en) * 2016-07-29 2022-08-19 알케마 인코포레이티드 Polyol pre-mix with improved shelf life
JP6826191B2 (en) * 2017-04-11 2021-02-03 オートリブ ディベロップメント エービー Polyurethane foam manufacturing method, steering wheel manufacturing method and steering wheel
EP3679108B1 (en) * 2017-09-05 2022-03-09 Huntsman Petrochemical LLC Catalyst system for polyol premixes containing hydrohaloolefin blowing agents
US10525663B2 (en) * 2017-09-28 2020-01-07 Johns Manville Foam insulation with improved low temperature properties
EP3688060A1 (en) * 2017-09-28 2020-08-05 Dow Global Technologies Llc Polyurethane rigid foam system with enhanced polyol shelf life and stability
CN108276546A (en) * 2017-12-28 2018-07-13 青岛海尔股份有限公司 Polyurethane rigid foam plastic and preparation method thereof
US10752725B2 (en) 2018-04-24 2020-08-25 Covestro Llc Rigid polyurethane foams suitable for use as panel insulation
US10640600B2 (en) 2018-04-24 2020-05-05 Covestro Llc Rigid polyurethane foams suitable for use as panel insulation
CN109294218A (en) * 2018-09-28 2019-02-01 上海东大聚氨酯有限公司 Combined polyether, polyurethane foam feedstock composition, from its polyurethane foam and its preparation method and application
US11053340B2 (en) 2019-03-08 2021-07-06 Covestro Llc HCFO-containing isocyanate-reactive compositions, related foam-forming compositions and PUR-PIR foams
US11161931B2 (en) 2019-03-08 2021-11-02 Covestro Llc Polyol blends and their use in producing PUR-PIR foam-forming compositions
US10851196B2 (en) 2019-04-29 2020-12-01 Covestro Llc Rigid polyurethane foams suitable for use as panel insulation
US11932761B2 (en) 2021-02-08 2024-03-19 Covestro Llc HFCO-containing isocyanate-reactive compositions, polyurethane foams formed therefrom, and composite articles that include such foams
US11827735B1 (en) 2022-09-01 2023-11-28 Covestro Llc HFO-containing isocyanate-reactive compositions, related foam-forming compositions and flame retardant PUR-PIR foams

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1095076A (en) * 1992-11-10 1994-11-16 大金工业株式会社 The decomposing inhibitor and the inhibition decomposition method thereof that are used for the halohydrocarbon of hydrogeneous and fluorine
CN101517032A (en) * 2006-09-01 2009-08-26 纳幕尔杜邦公司 Ascorbic acid, terephthalate, or nitromethane stabilizers for fluoroolefins

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6067524A (en) * 1983-09-22 1985-04-17 Mitui Toatsu Chem Inc Improvement of heat resistance of extremely soft polyurethane elastomer
US6753357B2 (en) * 2001-12-18 2004-06-22 Foam Supplies, Inc. Rigid foam compositions and method employing methyl formate as a blowing agent
US20110152392A1 (en) * 2009-12-17 2011-06-23 Honeywell International Inc. Catalysts For Polyurethane Foam Polyol Premixes Containing Halogenated Olefin Blowing Agents
US9695267B2 (en) * 2009-08-11 2017-07-04 Honeywell International Inc. Foams and foamable compositions containing halogenated olefin blowing agents
JP2009013247A (en) * 2007-07-03 2009-01-22 Central Glass Co Ltd Stabilized premix for rigid polyurethane foam
US20090099273A1 (en) * 2007-10-12 2009-04-16 Williams David J Non-silicone surfactants for polyurethane or polyisocyanurate foam containing halogenated olefins as blowing agents
US9453115B2 (en) * 2007-10-12 2016-09-27 Honeywell International Inc. Stabilization of polyurethane foam polyol premixes containing halogenated olefin blowing agents
US20090270522A1 (en) * 2008-04-25 2009-10-29 Honeywell International Inc. Blowing agents for polymeric foams
US20100016457A1 (en) * 2008-07-16 2010-01-21 Bowman James M Hfo-1234ze mixed isomers with hfc-245fa as a blowing agent, aerosol, and solvent
JP2014506947A (en) * 2011-02-21 2014-03-20 ハネウェル・インターナショナル・インコーポレーテッド Polyurethane foam premix containing halogenated olefin blowing agent and foam produced therefrom
CN103415543B (en) * 2011-03-11 2017-02-15 阿科玛股份有限公司 Improved stability of polyurethane polyol blends containing halogenated olefin blowing agent

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1095076A (en) * 1992-11-10 1994-11-16 大金工业株式会社 The decomposing inhibitor and the inhibition decomposition method thereof that are used for the halohydrocarbon of hydrogeneous and fluorine
CN101517032A (en) * 2006-09-01 2009-08-26 纳幕尔杜邦公司 Ascorbic acid, terephthalate, or nitromethane stabilizers for fluoroolefins

Also Published As

Publication number Publication date
EP2702088A1 (en) 2014-03-05
EP2702088B1 (en) 2018-05-16
JP2014511930A (en) 2014-05-19
WO2012141822A1 (en) 2012-10-18
JP5890895B2 (en) 2016-03-22
PL2702088T3 (en) 2018-08-31
CA2829347C (en) 2019-08-06
BR112013023136A2 (en) 2016-12-13
CN103415548B (en) 2017-05-17
CN106046411A (en) 2016-10-26
EP2702088A4 (en) 2015-11-04
BR112013023136B1 (en) 2020-12-15
ES2674330T3 (en) 2018-06-28
MX348762B (en) 2017-06-28
MX2013010406A (en) 2013-10-17
CN103415548A (en) 2013-11-27
CA2829347A1 (en) 2012-10-18
US20140051776A1 (en) 2014-02-20

Similar Documents

Publication Publication Date Title
CN106046411B (en) The improved stability of polyurethane polyol blend comprising halogenated olefin blowing agents
US10961339B2 (en) Stability of polyurethane polyol blends containing halogenated olefin blowing agents
CN104685021B (en) The improved stability of polyurethane polyol blend comprising halogenated olefin blowing agents
KR102292151B1 (en) Stabilized polyurethane polyol blends containing halogenated olefin blowing agent
CN107090090A (en) Improve the method for the stability of the polyurethane polyol blend containing halogenated olefins foaming agent
KR102433944B1 (en) Polyol pre-mix with improved shelf life

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant